Mildness additive

ABSTRACT

THE DEGREE OF SKIN IRRITATION OF DETERGENT COMPOSITIONS IS REDUCED BY ADDING SMALL AMOUNTS OF COMPOUNDS HAVING AT LEAST TWO POLAR GROUPS, E.G. HYDROXYL, CARBOXYL, ESTER, AMINO, AND AMIDO GROUPS SEPARATED BY AN ORGANIC RADICAL OF AT LEAST 15 CARBON ATOMS WHICH CONTAINS A CYCLIC GROUP. IN PARTICULAR, VARIOUS ALIPHATIC, AROMATIC AND HETEROCYCLIC AMINO, AMIDO AND ESTER DERIVATIVES OF POLYMERIZED FATTY ACIDS ARE DISCLOSED.

United States Patent Oflice 3,769,242 Patented Oct. 30, 1973 US. Cl.252-542 23 Claims ABSTRACT OF THE DISCLOSURE The degree of skinirritation of detergent compositions is reduced by adding small amountsof compounds having at least two polar groups, e.g. hydroxyl, carboxyl,ester, amino, and amido groups separated by an organic radical of atleast 15 carbon atoms which contains a cyclic group. In particular,various aliphatic, aromatic and heterocyclic amino, amido and esterderivatives of polymerized fatty acids are disclosed.

This application is a division of application Ser. No. 696,509, filedJan. 9, 1968, now Pat. No. 3,630,934, which is a continuation-in-part ofapplication Ser. No. 613,095 filed Feb. 1, 1967, now Pat. No. 3,538,009.

The present invention relates to mildness additives which prevent orreduce skin irritation, to compositions which contain a mildnessadditive that presents or reduces skin irritation, and to methods forpreventing or reducing skin irritation resulting from contact withirritating compositions by modification of the keratin layer of theskin.

A majority of cases of skin irritation can be traced back to a contactof the skin with a chemical composition containing a detergent. This is,in part, due to the nature of the detergent itself and, in part, due tothe action of the detergent in weakening the resistance of the skin.Most detergents intrinsically irritate the skin, although the degree ofirritation will vary significantly with the detergent. Such irritationcan result when the skin is contacted with an aqueous solution of suchdetergent or when such detergent is retained by a fabric on washing withsuch detergent which then comes into contact with the skin. As a resultof such skin irritation, many otherwise useful detergents are excludedfrom applications where such detergents come into contact with the skin.In some detergent compositions, e.g. dishwashing liquids and shampoos, acertain degree of skin irritation can be tolerated and is accepted,although not desirable.

The cause for this irritation is not clearly understood, but it isbelieved that detergents have a denaturing effect on the keratin layerof the skin. As a result thereof, other chemicals which normally do notirritate the skin when combined with a detergent can penetrate the skinand cause irritation. Although numerous attempts have been made todevelop additives which reduce or eliminate skin irritation, theadditives developed have found only limited success for a very narrowrange of detergent compositions.

It is therefore an object of the present invention to prevent or reduceskin irritation resulting from contact of the skin with chemicalcompositions.

It is another object of the present invention to modify theprotein-keratin layer of the skin to prevent or reduce skin irritationwhen contacted with chemical compositions which irritate the skin.

It is a further object of the present invention to provide modifiedcompositions used in contact with the skin, in

which the modification prevents or reduces skin irritation which wouldotherwise occur.

It is still another object of the present invention to providedetergent-containing compositions to which a mildness additive has beenadded whichprevents or reduces skin irritation which would otherwiseresult from the presence of such detergent.

Other objects will become apparent from the following description andclaims.

The prevention or reduction in skin irritation is achieved by contactingthe skin with a mildness additive having the general formula wherein Ris a divalent organic radical containing a chain of at least 15 atomsbetween the open valences of the radical, the majority of which arecarbon atoms, and containing a cyclic moiety of at least 5 atoms, andwherein Y and Y are polar groups; said mildness additive or its saltbeing soluble or colloidally dispersible in an aqueous phase or organicsolvents or other suitable media; the polar groups of the mildnessadditive being compatible with those of the irritant and stable inaqueous media. The term dispersible is meant to define colloidaldispersibility of the mildness additive in concentrations in which themildness additive is employed in actual use. The term polar group ismeant to define a group having a dipole moment and containing at leastone nitrogen, oxygen, phosphorus, sulfur or combinations thereof. Thesegorups are deemed to be capable of hydrogen bonding with the protein,although the formation of stronger bonds such as covalent bonds is notexcluded. The cyclic moiety is preferably a carbocyclic i.e., cyclichydrocarbon moiety of 5 to 18 carbon atoms which can be saturated or cancontain from 1 to 9 double bonds and can contain one or moresubstituents on the ring. Heterocylic moieties which contain thestructures O-, S, N-, or NH- in the ring can also be present in themildness additive and serve as the necessary cyclic moiety. Hetero-atomsare useful.

In accordance with the present invention, it was discovered that skinirritation and other more severe forms of dermatitis caused by thecontact of chemicals with skin can be reduced if not eliminated bycontacting the skin with a mildness additive as defined above. Thisreduction or elimination of skin irritations occurs regardless ofwhether the mildness additive is applied to the skin prior to orsimultaneously with the irritating chemical. Rinsing of the skin withwater or a mild soap solution after application of the mildness additivebut prior to the application of the irritant does not cause asignificant change in the effect of the mildness additive when a skinirritant is subsequently applied. This and other types of evidence, suchas electrophoretic studies of mixtures of soluble proteins and mildnessadditives, have shown that some form of interaction occurs between thekeratin layer of the skin and the mildness additive. Although thecomplex formed between protein molecules and the mildness additive canbe isolated by the indicated electrophoresis, the specific nature of thecomplex has not yet been established. It is presumed, however, that bothadsorption and some form of chemical interaction are involved. -It isfurther theorized that the cyclic structure in the mildness additiveaids in the adsorption of the additive onto the keratin layer of theskin and that the polar groups of the mildness additive interact withthe protein molecules of the keratin layer. In addition to the mildnessadditive containing at least two polar groups, the polar groups of themildness additive must also be separated by a chain of at least 15atoms, a majority of which should be carbon atoms. However, the presenceof additional polar groups located intermediary to the described twoterminal polar groups does not appear to interfere in the mildnesselfect of the additive. It is believed that as a result of this chainlength, the indicated polar groups are capable and do interact withdifferent protein molecules. The irritation of the skin by the action ofa detergent or other irritant is believed to be caused by thepenetration of the detergent into the skin, causing separation and/ ordegradation of the protein molecules of the keratin layer, therebyexposing the living cells of the skin to the detergent and, moresignificantly, exposing these cells to other, more irritating compoundsassociated with the detergent. The damage to the cells caused by thecontact is believed to result in irritation, inflammation, anddermatitis. The mildness additives employed in the detergentcompositions of the present invention are believed to counteract thisbreakdown by providing additional bridges between the protein moleculesof the keratin layer, which maintain the integrity of the skin surfacethereby preventing the penetration of the detergent molecules throughthe keratin layer into the living tissue. It is to be understood,however, that we do not wish to be bound by the foregoing explanation ofthe activity of the mildness additives of the present invention, andthat such explanation is only set forth for a better understanding ofthe present invention.

The mildness additives of the present invention contain at least twopolar groups separated by an organic radical of at least 15 atoms, amajority of which are carbon, and which contain a cyclic group. Thepolar groups should be compatible with the detergent and should be ofthe type capable of existing in the aqueous phase, i.e. withoutirreversibly reacting with the water. Additional polar groups may bepresent in this divalent radical or may be located on branches attachedto this radical. Such additional polar groups do not interfere in theeffectiveness of the mildness additive. The two polar groups descirbedcan be the same or different. Suitable polar groups include hydroxyl(-OH); carboxyl (--COOH); ester (R'OCO, wherein R can be an aliphatic,cycloaliphatic, or aromatic radical of 1-12 carbon atoms, or can be partof a polyester chain); amino (-NH substituted amino (NI-IR" or -NRR"',wherein R" and R' are aliphatic or aromatic hydrocarbon radicals of 1-12carbon atoms, or wherein R and R can combine to form 3- to 6-memberedrings with the nitrogen, or wherein R" is part of a polyamine chain);amido t (R"NH-( ior R R N-dwherein R and R are aliphatic or aromatichydrocarbon radicals of 1-12 carbon atoms and R can be part of apolyamide chain); quaternary ammonium salts eelwhere R, R and RVIII arelower alkyl radicals and X is an anion such as a halogen ion); sulfate(SO Me, where Me is a metal and preferably an alkali metal); sulfonate(-SOgMe); sulfonamide (-SO N-H2); substituted sulfonamide (-SO NHR or SONR R thio acid salts (-COSMe); thioesters (Real) substituted amido inionic form, carbon and oxygen or carbon and nitrogen. In generalfunctional groups of greater polarity are preferred over those of lesserpolarity. It will be apparent that the size of any of the describedsubstituents and particularly hydrocarbon substituents on the polargroup will affect the polarity. In general, the preferred substituentson the polar groups are lower alkyl groups and such water-solubilizinggroups as polyoxyalkylene radicals, in particular polyethylene glycolchains.

The effectiveness of the mildness additive in preventing skin irritationnot only requires the presence of at least two polar groups in themildness additive but also the separation of the polar groups by an atomchain of at least 15 atoms, the majority of which are carbon atoms. Theuse of shorter chain lengths does not result in a reduction of theirritating eflfect of a detergent. The presence of additional polargroups does not interfere in the function of the two polar groupsseparated by the necessary number of atoms, regardless of whether thesepolar groups are part of such chain or located on side branches of themolecule. The presence of more than two polar groups each of which areseparated by 15 or more atoms increases the eflectiveness of a mildnessadditive in which the polar groups are weak polar groups, such ashydroxyl groups, but does not appear to add significantly to theeffectiveness of a mildness additive containing at least two strongpolar groups such as carboxyl groups separated by the necessary linkingchain.

Although the minimum size of the linking radical is determined by thelength of the chain separating the polar groups, the maximum size of thelinking radical is determined by the dispersibility of the mildnessadditive in which it is incorporated. Thus compounds which are notliquid or colloidally 'dispersible are not suitable in preventing skinirritations. Hence, the upper limit of the size of the linking radicalis determined not only by the number of atoms in the linking radical,but also by the presence of additional polar groups in the linkingradical which can increase the dispersibility of the mildness additive,as well as the nature of any radical attached to the polar group. Ingeneral, however, the linking ra'dical contains less than atoms. Asindicated, the linking radical has, preferably, a carbon backbonestructure which can be aliphatic, cycloaliphatic, or aromatic in nature.The required carbocyclic or heterocyclic moiety need not be part of thebackbone structure. Particularly effective are hydrocarbon linkingradicals which contain a cycloaliphatic or aromatic ring structure. Inaddition to the preferred hydrocarbon structure, the linking radical canalso be in the form of polymeric structure such as a polyester,polyether, polyamide, or polyamine. Although other polymeric linkingradicals will be apparent to those skilled in the art, many of theseradicals are excluded by virtue of the limitations with respect tosolubility or colloidial dispersibility required to give rise to themildness-inducing properties. The preferred polymeric linking radicalsare the polyether radicals derivable from polyoxyalkylene ethers,containing 2 to 30 oxyalkylene units in which the alkylene radicalcontains from 2 to 4 carbon atoms. The polyoxyalkylene units can, inaddition, contain ester groups. Thus, suitable linking radicals areobtained by the reaction of a polyoxyalkylene glycol with apolycarboxylic acid.

The preferred mildness additives employed in combination with skinirritants are the polymerized, ethylenically unsaturated C -C fattyacids and polar group-containing derivatives thereof. Generally, thepolymerized fatty acids contain from 2 to 4 monomeric acid units, and,consequently, from 2 to 4 carboxyl groups. The polymeric fatty acids canbe employed as such as mildness additives or the carboxyl groups can bealtered by known chemical reactions into other polar groups, such as byesterification, amidation, and the like. The polymerization ofethylenically unsaturated fatty acids into dimer, trimer, and tetrarneracids is known in the art a gene!- ally results in a cycloaliphatic ringstructure. Thus, the dimer acid derived from linoleic acid has thestructure, which can exist in the cis and trans forms, of

The dimer, trimer, and tetramer acids are commercially available. Itwill be apparent, in view of the foregoing discussion, that the mildnessadditive need not be pure, but that a mixture of mildness additives canbe employed such as a mixture of dimer and trimer acids, and that themildness additive can, furthermore, contain compounds which do not addto the mildness properties of the additive such as unpolymerized fattyacids. Van'- ous polar groups can be substituted for the carboxyl groupsof polymerized fatty acids as described above. Suitable mildnessadditives which are based on a fatty acid dimer linking radical includethe following in which [D] represents the carboxyl-free residue of adimerized fatty acid and [T] represents the carboxyl-free residue of atrimer acid:

ECH2OH] Other specific mildness additives which are not based on apolymerized fatty acid are cycloaliphatic or aromatic dicarboxylic acidsand derivatives thereof which contain at least 15 carbon atoms betweenat least two polar groups and which are soluble or dispersible. Polymerswhich are based on repeating cycloaliphatic or aromatic acid moietiesand which are soluble or dispersible, are also suitable. Such polymersare, in particular, polymers derived by the reaction of polyoxyalkyleneglycols with cyclic dicarboxylic acids such as benzene dicarboxylicacids, dihydrophthalic acids, tetrahydrophthalic acids,cyclohexanedicarboxylic acids. Others include reaction products of suchacids with diamines or polyamines. Still another class of suitablecompounds includes alkylene oxide addition products to polyolscontaining cycloaliphatic or aromatic moieties.

The mildness additives described herein above can be employed incombination with any detergent that is anionic, cationic, nonionic, oramphoteric in nature. It will be apparent, however, that the polargroups of the mildness additive should be compatible with those of thedetergent to avoid insolubilization of both detergent and additive. Thereduction of skin irritation will be observable in all compatiblecombinations, although the extent of the anti-irritant effect willdiffer with the various mildness additives discussed, as well as withthe detergent. Since some of the detergents, particularly nonionicdetergents, are by themselves relatively non-irritating, the describedmildness additive is less useful, although the mildness effect of theadditive can be established when such detergents, which at normally usedconcentrations cause little or no skin irritation, are tested at highconcentrations and/or longer periods of contact with the skin.

The anti-irritation effect of the mildness additive is exhibited over awide range of proportions of additive to detergent as indicated above.However, optimum results are generally obtained when the ratio ofdetergent to mildness additive is in the range of 3:1 to 1:3. Thispreferred range is applicable regardless of whether the detergent isemployed in a dilute or concentrated form.

Anionic detergents which are improved by combination with the describedmildness additives include both the soap and the non-soap detergents.Examples of such soaps are the sodium, potassium, ammonium, andalkylolammonium salts of higher fatty acids (C to C Nonsoap anionicdetergents with which the described mildness additives are suitablyemployed include alkyl sulfates, alkyl sulfonates, alkyl benzenesulfonates, alkyl phenyl polyoxyalkylene sulfonates, alkyl glycerylether sulfonates, alkyl monoglyceride sulfates, alkyl monoglyceridesulfonates, alkyl polyoxyethylene ether sulfates, acyl sarcosinates,acyl esters of isothionates, acyl-N-methyl taurides, dialkyl esters ofsulfosuccinic acid, and mixtures thereof. In these non-soap detergents,the alkyl or acyl radicals contain from 9 to 20 carbon atoms. As in thesoaps, these detergents are employed in the form of sodium, potassium,ammonium, and alkylolammonium salts, as well as similar water-solublesalts. Specific examples include sodium lauryl sulfate,potassium-N-methyl lauroyl tauride, triethanol-ammonium dodecylsulfonate, potassium polypropylene benzene sulfonate, sodium laurylsulfonate, dioctyl ester of sodium sulfosuccinic acid, sodium salt oflauryl polyoxyethylene sulfate, and sodium salt of tridecyletherpolyoxyethylene sulfate.

The cationic detergents which can be reduced in their skin irritation bythe addition of the mildness additives of the present invention include,in particular, quaternary ammonium salts which contain at least onealkyl group having from 12 to 20 carbon atoms. Although the halide ionsare the preferred anions, other suitable anions in clude acetate,phosphate, sulfate, nitrite, and the like. Specific cationic detergentsinclude distearyl dimethyl ammonium chloride, stearyl dimethyl benzylammonium chloride, stearyl trimethyl ammonium chloride, coco dimethylbenzyl ammonium chloride, dicoco dimethyl ammonium chloride, cetylpyridinium chloride, cetyl trimethyl ammonium bromide, stearyl aminesalts that are soluble in water such as stearyl amine acetate andstearyl amine hydrochloride, stearyl dimethyl amine hydrochloride,distearyl amine hydrochloride, alkyl phenoxyethoxyethyl dimethylammonium chloride, decyl pyridinium bromide, pyridinium chloridederivative of the acetyl amino ethyl esters of lauric acid, lauryltrimethyl ammonium chloride, decyl amine acetate, lauryl dimethyl ethylammonium chloride, the lactice acid and citric acid and other acid saltsof stearyl 1 amido-imidazoline with methyl chloride, benzyl chloride,chloroacetic acid and similar compounds, mixtures of the foregoing, andthe like.

Amphoteric, also referred to as ampholytic, detergents which can beimproved by the addition of the described mildness additives includealkyl- 3-iminodipropionate, alkyl-fl-aminopropionate, fattyimidazolines, betaines, and mixtures thereof. Specific examples of suchamphoteric detergents are l-coco-S-hydroxyethyl 5 carboxymethylimidazoline, dodecyl-fi-alanine, the inner salt of Z-trimethylaminolauric acid, and N-dodecyl-N,N-dimethyl aminoacetic acid.

As indicated above, the mildness additives of the present invention canalso be employed in combination with nonionic detergents although thebeneficial effects of the addition of the mildness additive are lesspronounced since nonionic detergents are inherently not as irritating asthe above-described detergents. Nonionic detergents include, inparticular, the alkylene oxide ethers of phenols, fatty alcohols, andalkyl mercaptans, the alkylene oxide esters of fatty acids, the alkyleneoxide ethers of fatty acid amides, the condensation products of ethyleneoxide with partial fatty acid esters, and mixtures thereof. Thepolyoxyalkylene chain in such agents can contain from 5 to 30 alkyleneoxide units in which each alkylene unit has from 2 to 3 carbon atoms.Specific examples of nonionic detergents include nonyl phenolpolyoxyethylene ether, tridecyl alcohol polyoxyethylene ether, dodecylmercaptan polyoxyethylene thioether, the lauric ester of polyethyleneglycol, the lauric ester of methoxy polyethylene glycol, the lauricester of sorbitan polyoxyethylene ether, and mixtures thereof.

The mildness additives of the present invention are particularlyeffective in reducing the irritation caused by such anionic detergentsas the alkyl sulfates and sulfomates and the alkyl benzene sulfates andsulfonates, and by such cationic detergents as the described fattyalkylcontaining quaternary ammonium compounds.

Many of the detergents described hereinabove are employed in theircommercial applications in combination with builders or other additives,depending on the intended commercial utility of the detergent. Thepresence of such additives does not affect the ability of the mildnessadditive to counteract the skin irritation caused by the detergent. Asindicated above, it is believed that the skin irritation is caused bythe action of the detergent on the skin in causing the keratin of theskin to break down. Although the detergent itself may not be extremelyirritating, it allows other materials employed in combination with thedetergent which are highly irritating to come in contact with the livingtissue of the skin, even though in the absence of the detergent suchmaterials are non-irritating in not being able to break down the keratinof the skin. The mildness additives of the present invention are,therefore, capable of protecting the skin against skin irritation causedby such additives. Builders employed in commercial detergentformulations are generally alkali salts of weak inorganic acids usedalone or in admixtures, such as alkali metal, ammonium or substitutedammonium salts of carbonates, borates, phosphates, polyphosphates,bicarbonates, and silicates. Specific examples of such salts are sodiumtripolyphosphate, sodium carbonate, sodium tetraborate, sodiumpyrophosphate, sodium bicarbonate, potassium bicarbonate, sodium monoanddi-orthophosphate, sodium metasilicate, and mixtures thereof.

The built detergent compositions of the present invention can,furthermore, contain other adjuvants normally employed in detergentcompositions such as perfumes, anti-tarnishing agents, anti-redepositionagents, bacteriostatic agents, dyes, fiuorescers, fabric softeners,oxygen or chlorine bleaches, suds builders, suds depressors,sequestrants, and the like. The inorganic builders or the combination ofthe builders and the adjuvants described can constitute up to of thebuilt detergent composition, the remainder of the built detergentcomposition being the detergent and the mildness additive.

The detergent compositions of the present invention include laundrydetergents, kitchen detergents, shampoos, industrial detergents, and thelike. The use of the mildness additive of the present invention does notaffect the effective concentrations of the detergent, and henceconcentrations of detergents heretofore employed are also applicable inthe modified compositions of the present invention.

The use of the mildness additive is, however, not limited to unbuilt orbuilt detergent compositions. The additive can be employed in anycompositions in which a detergent of the type described is employed inthe presence of other materials which may cause skin irritation such as,in particular, in lubricants containing inorganic salts, a particularexample of which are cutting fluids. The protection against skinirritations is further not limited to detergents and extends to a widevariety of skin irritants, including such as are contained indeodorants, disinfectants, polishes, hair preparations, cleaningcompositions, etc. The irritant can be inorganic in nature, or organic.In view of the foregoing explantation, this is not surprising since theprotection derived from the mildness additive is based on theinteraction of such with the keratin layer of the skin and not oninteraction with the irritant. Because of this interaction, it isfurthermore unnecessary to combine the mildness additive with theirritant in order to achieve the protection of the skin. Thus, themildness additive can be applied to the skin prior to any contact withan irritant and will protect the skin against subsequent irritation fora long period of time.

In establishing the irritations and the mildness effect of the additive,the skin is contacted by immersion or other means with a solutioncontaining the irritant with and without the mildness additive understandardized conditions more specifically described below. The principaltest employed in the data presented below is an animal immersion testusing female, albino guinea pigs. The animal, weighing about 300 to 325g., is immersed up to the thoracic region in the test solution at 40 C.for 4.5 hours per day on three successive days. Each animal isthoroughly rinsed and dried after each immersion. Three days after thelast immersions, the skin of each animal is examined for gross changes,and grades are assigned which represent the degree of damage to theskin. In general, three animals are tested simultaneously in the samesolution. The grading system is based on a scale of 1 to 10, in whichthe numbers have the following meanmgs:

Grade or rating Gross reaction Skin damage 1. Severe cracking andbleeding; death of Extremely severe;

animal in most instances. death of skin tissue. 2 Severe cracking;moderate bleeding. Do. 3 Severe cracking; slight to moderate Severe.

bleeding. 4 Moderate cracking Do. 1 Slight cracking Moderate. 5 Severescaling Do. 6.- Edema; slight to moderate scalin 7- Sl ght scaling andmoderate edema. Slight Slight redness and edema- Do. Normal Normal.

Despite the fact that this exposure test is conducted using extremelydilute solutions, it is an exaggerated test, as compared to humanexposure; although it has been established (see Can, Pat, 639,398) thatthe test correlates extremely well with the skin irritation effectobserved on human skin.

In preparing the test solution, a 100 g. concentrate is first preparedwhich is then employed in the test solution in 1% by volumeconcentrations. In order to prepare a homogeneous concentrate which isreadily dilutable, the following additional ingredients were added asindicated: Igepal CA-630, a commercially available nonionic wettingagent of octylphenoxypoly(oxyethylene)ethanol; triethanol amine, andcapric acid. The triethanol amine (TEA) is employed to allow saltformation of mildness additives employed in combination with anionicdetergents and the capric acid (Cap. A) is employed for the same purposein combination with cationic detergents. In general, the detergent andthe mildness additive are each employed in the examples illustratedbelow in a concentration of 15 weight percent based on the described 100g. concentrate. Where a built detergent is employed, the amount ofdetergent is accordingly adjusted to take into consideration the loweractive detergent concentration.

The following examples illustrate the elfect of the mildness additivesof the present invention on skin irritation cause by detergents, usingthe above-described test.

The detergent was employed in 100% active form or in 87% active form,the latter form containing sodium sulfate. The mildness additivesemployed in this series comprised the dimer of linoleic acid,commercialy available as Empol 1022, and derivatives of the dimer acid.The dimer acid contained 2-5% of unpolymerized linoleic acid and 19-22%of trimer acid. The dimer ester was prepared from the dimer acid byesterification with a polyethylene glycol having a molecular weight of400 in a molar ratio of acid-to-polyether of 1:125 until an acid numberof 5 was obtained. The dimer amide employed is the reaction product ofone mole of dimer acid with 4 moles of diethanol amine. The dimermorpholide employed is the reaction product of 4 moles of morpholinewith one mole of dimer acid. The dimer amine employed is a commerciallyavailable compound in which the carboxyl groups of the dimer acid arereplaced by amino methyl (CH NH groups. Table I illustrates the resultsobtained employing the above-described test. The actual composition ofthe solution to which the animals were exposed is shown. The remainderof the composition of the test solution not indicated in the table waswater.

TABLE I.ALKYL BENZENE SULFONA'IE EXPOSURE Detergent Dimer additive Otheradditive Ratio 01' Percent Percent Percent Improvedetergent concen-Percent ooncenconcen- Average ment in to mildness Example No. trationactive Type tration Type tration rating rating additive 0.15 87 Igepal.4 0.15 87 9 5 0.15 87 8 4 0.15 87 9 5 g. Death' 7 7 0. 176 100 Death ni3-132 as 8 8 8 8 0.176 100 9 9 0i 176 100 Morph 8+ 8+ 0.15 87 Diamine 95 EXAMPLES 1 TO 12 EXAMPLES 13 TO 32 The tests and determination ofresults illustrated in CHOnHn Examples 1-12 were repeated using sodiumlauryl su1- fate instead of the alkyl benzene sulfonate. The results 50are illustrated in Table 11.

SO -Na+ TABLE IL-SODIUM LAURYL SULFATE EXPOSURE Detergent Dimer additiveOther additive Ratio 0! Percent Percent Percent Improvedetergent concen-Percent coneenconeen- Average ment in to mildness Example No. trationactive Type tration Type tration rating rating additive Death Diamine.

1 1 1 2 EXAMPLES 33 TO 37 The concentrate contained 22.5% of theAmphicide and was employed as a 2% test solution containing The testsand determination of results illustrated in 0,45% Amphicide" andresulted in an average rating of Examples Wm? repeated using a pdetergent, 5. The average rating was improved to 9 by the addition i.e.,the triethanol amine salt of lauric acid. Although the f 0,15% f di idnd 0.10% of t iethanol amine detergent is reltively mild at a 1% ofconcentrate level, 5 t th test l ti i.e., 0.15% in test solution, themildness elfect of the additive is particularly shown when the detergentis em- EXAMPLES 43 To 46 ployed in higher concentrations. The resultsare illus- The tests and determination of results illustrated in tratedin Table III. Examples 1-12 were repeated using Orvus AB, a com- TABLEIIL-TEA-LAURATE EXPOSURE Detergent Dimer additive Other additive Ratioof Percent Percent Percent Improvedetergent coneen- Percenteoncenconcen- Average ment in to mildness Example No. tratiou activeType tration Type tration rating rating additive 0.15 100 TEA 0.05 7+0.15 100 Acid 0.15 TEA 0.15 8+ 1 1:1 0.15 0.15 TEA 0.063 9- 2 1:1 0.150.15 TEA 0.003 9- 2 1:1 0.45 0 TEA 0.18 Death 0.45 100 Acid 0.45 TEA0.45 7+ 7+ 1:1

EXAMPLES 39 AND 40 mercially available linear alkane sulfonate detergentcontaming 40% of a linear alkane sulfonate, 43% of sodium The tests anddetermination of results illustrated in sulfate, and of sodium chloride.The following re- Examples 1-12 were repeated using a commerciallyavailsults were obtained (Table IV).

TABLE IV.-ALKANE SULFONATE EXPOSURE Detergent Dimer additive I Otheradditive Ratio 0! Percent Percent Percent Improvedetergent concen-Percent concenconcen- Average ment in to mildness Example No. trationactive Type tration Type tration rating rating additive 0.375 Death0.375 40 Acid 0.15 TEA 0.10 7 7 1:1 0.375 40 Ester 0.15 TEA 0.02 s a 1:10.375 40 Amide 0.15 7 7 1:1

able amphoteric detergent Deriphat 151 C containing EXAMPLES 47 AND 50N-eoco-B-aminopropionic acid. The active component of The tests anddetermination of results illustrated in the detergent was 70%; it wasemployed in the concen- Examples 1-12 were repeated using Orvus K, acomt ate In a cflmielltffitloll of A (Containing mercially availablemodified ammonium lauryl sulfate 046% of the f p 151 soluflofl u d the40 detergent containing an amide builder having the followdeaths of theanimals in the descrlbed immersion test. i i i When dimer acid (0.15% oftest solution) and triethanol percent amine (0.10% of test solution)were added, the rating of Alk ulf t 37 5 skin irritation improved to anaverage of 9 Alkanol amide 92 Unsulfated alcohol 1.2 EXAMPLES 41 AND 42Ammonium sulfate 0.9 The tests and determination of results illustratedin g g i a fg fiz g' Examples 1-12 were repeated using a commerciallyavaily able amphoteric phenolic detergent commercially avail- Thefollowlng results were obtained (Table V).

TABLE V.AMMONIUM LAURYL SULFATE EXPOSURE Detergent Dimer additive Otheradditive Ratio 01 Percent Percent Percent Improvedetergent concen-Percent ooncenconcen- Average ment in to mildness Example No. trationactive Type tration Type tration rating rating additive 0.40 37.5 0.4037.5 Acid 9- 3- 1:1 0.40 37.5 listen. 8 2 1:1 0.40 37.5 Amide 9- 3- 1:1

able as A mphicrde containing in 75% concentration EXAMPLES 51 To 54 thefollowing active components: 1 part of the sodium salt of2-[(2-hydroxy-5-nonylben- The tests and determination of resultsillustrated in zene)methylamino]ethane sulfonic acid, and Examples 1-l2were repeated using Standpol ES-Z, a 3-parts of the sodium salt of2-[(3-dimethylaminomethylcommercially available 26% active detergentcontaining 2 -hydroxy 5 nonylbenzyl)methylamino]ethane sulthe sodiumsalt of lauryl C through C diether sulfate. fonic acid. The followingresults were obtained (Table VI).

TABLE VI.-LAURYL DIETHER SULFATE EXPOSURE Detergent Dimer additive Otheradditive Ratio 01 Percent Percent Percent Improvedetergent coneen-Percent concenconeen- Average merit in to mildness Example No. trationactive Type tration Type tration rating rating additive 2e 5 2e Acid0.15 TEA 0.10 8+ 3+ 1:1 26 Ester 0.15 8+ 3+ 1:1 0.15 8+ 3+ 1:1

26 Amide 13 EXAMPLES 55 TO 58 The tests and determination of resultsillustrated in Examples 1-12 were repeated employing a cationicdetergent commercially available as Hyamine 2389 containing 40%methyldodecylbenzyl trimethyl ammonium chloride,methyldodecylxylylene-bis(trimethylammonium chloride), and 50% water,and therefore determined to be 50% active. Test solutions containing0.30% of the detergent in the absence and in the presence of 0.151% ofthe below-listed dimer derivatives were Prepared and tested in thedescribed immersion test. The following results were obtained in which[D] represents the carboxyl-free residue of the dimer acid.

Average Example Additive rating 55 Death 56 7 D( C HzNHg) D-CHzN(C a)r58 7 [D (CHa-NH-CHz-CHz-CHr-NHn) EXAMPLES 59 TO 62 The tests anddetermination of results illustrated in Examples 1-12 and 13-16 wererepeated using a dimer glycol and a dimer sulfate as the mildnessadditive. The following results were obtained:

To a 1% solution of a shampoo commercially available as Prell was added2% by weight of the solution of the triethanol amine salt of the dimeracid of Examples 1-12. Using the above-described exposure test, a ratingof 7 was obtained. In the absence of the mildness additive the animalsexposed died.

EXAMPLE 64 A cutting fluid containing, per 100 parts of the solution, 4parts of the dimer acid ester of Example 3, 8 parts of sodium nitrile,10 parts of triethanol amine, and 1.5 parts of oleyl diethanol amide wasemployed in the above-described exposure test. A rating of 8+ wasobtained for the cutting fluid when tested at 17% concentration. In theabsence of the dimer ester ester the rating dropped to 4.

EXAMPLES 65 TO 86 The tests and determination of results illustrated inExamples 1 to 6 and 13 to 16 for anionic surfactants and in Examples 55to 58 for cationic surfactants were repeated using the indicatedmildness additive and surfactants in a concentration of 1%. Thefollowing results were obtained:

TABLE VIL-SODIUM LAURYL SULFATE-ALKYL BEN- ZENE SULFONATE EXPOSURESurfae- Average Example Mildness additlve tant rating 65 Ester;i ofdimer glycol and dimer SLS 7.8

aci 66 Amide of dimer diamine and 9.0

capric acid. 67- do 8.6 68 Trimer acid 7.8 69s 8.8 70. Polyester oftetrahydrophthalic 6.5

acid'and polyoxyethylene glycol (mol wt. 400) n=3 to 4 [average degreeof polymerization]. 71 Polyester of tetrahydrophthalic ABS 7.2

acid and polyoxyethylene glyc (mol wt. 400) n=3 to 4 [n= average degreeof polymerization]. 72 Dimer chloride 5.5 73--- do 6.8 74 Reactionproduct of dimer glycol 6.3

and toluene diisocyanate. 75-.- o 6.6 Dim er glycol diacetate 7. 5 o 5Reaction product of dimer acid 8.3

and (2-hydroxyethyl)ethylene diamine in mole ratio 1:2. tletlziylenediamine in mole ratio 8.3 79 Reaction product of dimer acid 8.3

and (2-hydroxyethy1) ethylene diamine in mole ratio 1:2. 80 Polyester oiisophthalic acid and 8 polyethylene glycol, (mol wt. 400) 11-3- to 4. 81do SLS 6.3 82 Polyester 0! phthalic anhydride SLS 5.6

and polyethylene glycol (ml. wt. 400) n 3 to 4. 83 Condensate ofhydrogenated dimer 8.9

acid with ethylene diamine. 84 -do ABS 9 85 Tetra-butyl-phosphonium saltof Hyamine.. 7.5

dimer acid. 86 11-856 (commercially available SLS 6.6

polyol esterified with oleic acid and ethoxylated).

1 SLS=Sodium lauryl sulfate. 9 ABS=Alkyl benzene sulfonate of Examples 1to 12.

EXAMPLES 87 TO 93 The exposure test illustrated in Examples 1 to 12 wasemployed sequentially to demonstrate that the mildness additiveinteracts with the skin to give rise to protection against irritation.Guinea pigs were immersed in a solution of the mildness additiveindicated in the table below for a period of 15 minutes. The animalswere then removed from the solution and thoroughly rinsed with tapwater. The animals were then reimmersed in a solution of the detergentindicated in the table for a period of 2.25 hours and thereafter rinsedand placed in their cages. This procedure was repeated for three daysand the animals were graded at the end of a three-day rest. Thefollowing results were obtained. In all instances the concentration ofthe mildness additive and the detergent were 0.15%.

TABLE VIII.-ALKYL BENZENE SULFONATE-SODIUM LAURYL SULFATE SEQUENTIALEXPOSURE Deter- Average Example Mildnass additive gent rating 87 ABS l5. 5 88- Triethanol amine salt of dimer acid- ABS 8. 5 89 Diethanolamideof dimer acid ABS 9. 0 90- Dimer morpholide ABS 9 91 Polyester of dimeracid and poly- ABS 8. 5

ethylene glycol (ml. wt. 400); polyester degree of polymerization 'n=3to 4. 92. SLS I 6. 0 93 Triethanolamine salt of dimer acid SLS 8. 0

i Alkyl benzene sult'onate of Examples 1 to 12. 2 Sodium lauryl sulfate.

The same results are obtained when the animals are exposed to themildness additive on only the first day and not on the subsequent days.Some reduction in skin irritation is furthermore obtained when themildness additive is employed after the skin is exposed to the irritant.

EXAMPLE 94 Three aqueous solutions containing respectively 0.08%tributyl tin oxide (TTO), 0.08% TI'O and 0.15% triethanol amine salt ofdimer acid (dimer soap), and 0.08% TTO and 0.15% of triethanolamine saltof oleic acid (oleic soap) were prepared. The oleic soap is considered amild detergent. These solutions were employed in the above describedanimal exposure tests. The following results were obtained:

Solution: Rating 0.08% TTO 5.5 0.08% TTO+0.15% oleic soap Death 0.08%TTO+0.15% dimer soap 8.5

EXAMPLE 95 The above described animal exposure tests were employed withthe below indicated solutions for an exposure time of 4.5 hours. Thefollowing results were obtained.

Solution: Rating Trisodium phosphate 1.0% Oleic soap 0.15% DeathTrisodium phosphate 1.0% 8 5 Dimer soap 0.15%

EXAMPLIE 96 No reaction Questionable erythema 1 Positive erythema 2Intense erythema 3 The added reaction results of all twelve subjectsafter about 24 hours and 48 hours from the start of the test were asfollows:

TABLE IX.PATCH TEST Concentration in Test weight After Aiter N 0.Composition percent 24 hrs. 48 hrs.

1 Sodium lauryl sulfate 8 20 22 Sodium lauryl sulfate 8 p usTl'iBlJlfi-HOIMMDB salt of dimer 8 3 13 am 3 Sodium lauryl sulfate..- 615 17 Sodium lauryl sulfate- 6 4 plus Trietianolamine salt of dimer 6 55 aci Sodium lauryl sulfate 6 5 p lTrietianolamine salt of oleic 6 15 am6 Sodium lauryl sulfate-.-.-.:.....-. 4 21 Sodium lauryl sulfate 4 7plus Tn'etranolamme salt of duner 4 5 7 aci The foregoing examples haveillustrated the mildness inducing effect of the mildness additives onthe keratin layer of the skin when such as exposed to a skin irritantbefore, during or after the application of the mildness additive. Inmany detergent-containing compositions the skin irritation caused by thedetergent is compounded by detergent builders or other componentspresent in the composition. The foregoing examples clearly demonstratethat the mildness agents employed in combination with the detergents areparticularly effective in reducing skin irritation where the skinirritation is compounded by the presence of other agents, organic orinorganic. In view of the fact that the overall chemical structure ofthe mildness additives of the present invention is similar to that of adetergent, it will be apparent that the mildness additives of thepresent invention can be employed in combination with a skin irritatingdetergent in any environment, i.e., in the presence of any component inwhich the detergent can exist. The foregoing examples further illustratethat the greatest benefit of the described invention is realized whenthe mildness additives are combined with detergents or withdetergent-containing compositions which cause skin irritation.

In view of the extreme diversity of skin irritants known today, it willbe apparent that a demonstration of reduced skin irritation of alldetergent compositions with the described mildness additives is notpossible. However, such is not deemed necessary and the foregoingexamples are deemed suificient to illustrate the scope of the inventionbut are not intended to limit the scope of the invention to such.

What is claimed is:

1. A detergent composition consisting essentially of a skin irritatingdetergent selected from the group consisting of anionic, cationic, andamphoteric organic detergents and .005 to 10 parts by weight per part byweight of said skin irritating detergent of a mildness additivecomprising (I) the substituted polymerized product of 2 to 4 moleculesof a monomeric C to C unsaturated fatty acid, wherein said polymerizedproduct contains a cyclohexene moiety and instead of 2 to 4 carboxylgroups from said fatty acid, radicals selected from the group consistingof and morpholido; in which R", R', R and R are aliphatic or aromatichydrocarbon radicals of 1-12 carbon atoms; or where R" and R' combine toform a 3 to 6-membered ring with the amino nitrogen; R R" and RVIII arelower alkyl radicals and X is an anion; or (II) the substitutedsaturated polymerized products defined in (I); said detergentcomposition exhibiting reduced skin irritation compared to the samecomposition absent the mildness additive; the mildness additive anddetergent being stable and compatible in aqueous media.

2. The detergent composition of claim 1 in which said radicals are -CHNR"H.

3. The detergent composition of claim 1 in which said radicals are CHNR"R"'.

4. The detergent composition of claim 1 in which said radicals are 0 -iJNH:

5. The detergent composition of claim 1 in which said radicals are 0 -i.ZNHR 6. The detergent composition of claim 1 in which said radicals are0 -ENRIVRV 7. The detergent composition of claim 1 in which saidradicals are vl -cH,-I I-R X Rvrn 8. The detergent composition of claim1 in which R", R', R and R are aliphatic hydrocarbon radicals of l12carbon. atoms.

9. The detergent composition of claim 1 in which R", R, R and R arealkyl radicals of 1-12 carbon atoms.

10. The detergent composition of claim 1 in which the mildness additiveis defined in I and in which said radicals are morpholido.

11. The detergent composition of claim 1 in which said mildness additiveis defined in I and said radicals are -CH NH 12. The detergentcomposition of claim 1 in which said mildness additive is defined in Iand said radicals are -CH N(CH 13. The detergent composition of claim 1in which said mildness additive is defined in I and in which saidradicals are CH --NHCH -CH CH NH 14. The detergent composition of claim1 wherein said mildness additive is selected from the group designated15. The composition of claim 1 wherein said mildness additive isselected from the group designated (II).

16. The composition of claim 1 wherein the detergent is an anionicdetergent.

17. The composition of claim 1 wherein the anionic detergent is alkylbenzene sulfonate, alkylsulfate, alkyl benzene sulfates, or alkylsulfonate.

18. The composition of claim 1 wherein the detergent is a cationicdetergent.

19. The composition of claim 1 wherein the cationic detergent is aquaternary ammonium compound.

References Cited UNITED STATES PATENTS 2,878,190 3/1959 Dvorkovitz eta1. 252544 3,166,548 1/1965 Kirkpatrick et al. 252 -544 X 3,318,8175/1967 Smith 252544 X 3,538,009 11/1970 Kelly et al. 252547 X 3,630,93412/1971 Kelly et a1. 252132 X 3,654,167 4/1972 Akrongold et al. 2521193,223,635 12/1965 Dwycr et al 25251.5

HERBERT B. GUYNN, Primary Examiner US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO.3,769,242 DATED I October 30, 1973 |NVENTOR(S) Ralph Kelly et al.

it is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

COLUMN LINE ERROR l 31 "presents" should read prevents 2 29 "gorups"should read groups 5 1o "(CH should read (CH 5 26 5 CH OR should read 540 "D[-coor\r' 9] should read D E cd 2 8 67-70 "1" should read 5 Column1 of the Table I "5" should read 6 "6" should read 7 "7" should read 8"8" should read 9 and "90" should read l0 UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTION PATENT NO. 3,769,242 PAGE 2 DATED October 30,1973 |NVENTOR(S) Ralph Kelly et al.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

COLUMN L II I ERROR 11 I l v "37" should read 38 14 23 Delete "ethylenediamine in mole ratio 4.16 31 Insert after "-CH NHCH CH CH NH 9 16 33 CHN should read 9 c NH Signed and Sealed this twenty-third Day ofSeptember 1975 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN

